Zeolite structure polyoxometallate-based metal organic framework material as well as preparation method and application thereof

Abstract

The invention provides a polyoxometallate-based metal organic framework material with a zeolite structure as well as a preparation method and application of the polyoxometallate-based metal organic framework material. The polyoxometallate-based metal organic framework material with the zeolite structure is prepared by the preparation method. The preparation method comprises the following steps: adding (NH4) 6Mo7O24. 4H2O, molybdenum powder and ZnCl2 into water to obtain a solution A; adding H3PO3, a template agent and an organic ligand to obtain a solution B; heating and reacting the solution B in a reaction kettle, cooling, collecting a head product, activating with water and ethanol, and drying. The polyoxometallate-based metal organic framework material with the zeolite structure is used for adsorbing rubidium ions. The zeolite structure polyoxometallate-based metal organic framework material is synthesized in situ through a one-step hydrothermal method, the reaction synthesis efficiency is improved, the problems that polyacid components are high in solubility and prone to agglomeration in an aqueous solution are solved, active components are evenly distributed and stably embedded in the material, and the adsorption performance of the material to rubidium ions is remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal-organic framework materials, and particularly relates to a zeolite-structured polyoxometalate-based metal-organic framework material, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of modern high-tech industries, the importance of the three major resources of rare earth metals, rare metals, and scattered metals has become increasingly prominent. Among many rare metal elements, the alkali metal element - rubidium is known as the "optoelectronic metal illuminating the future". Due to its good ductility, good electrical and thermal conductivity, strong chemical activity, and excellent optoelectronic effect performance, etc., it has shown great commercial value and broad development prospects in the rapid development process of high-tech industries. Therefore, the recovery of rubidium resources is of great significance.

[0003] As an important rare metal, the effective development and utilization of rubidium resources are of great significance to the development of high-tech industries. At present, the main source of rubidium is extracted from ores. Although this process is mature, there are problems such as complex processes. In the existing salt lake industrial production, usually potassium is extracted first, and then lithium is extracted. However, it has been found that almost no rubidium ions can be detected in the brine after potassium extraction, which causes serious loss of resources. Therefore, there is an urgent need to develop new technologies for recovering rubidium resources. There are abundant rubidium resources in salt lake brines, but due to problems such as low concentration and strong interference of coexisting alkali metal ions, most of the research on separating and extracting rubidium from brines remains at the experimental stage. Among many separation methods, considering aspects such as efficiency, cost, and environmental requirements, the adsorption method is still an important way to separate and extract rubidium.

[0004] Polyoxometalate (POM), abbreviated as polyacid, is a class of nano-scale metal-oxygen cluster compounds formed by the connection of pre-transition metals and central heteroatoms through bridging oxygen bonds. Polyoxometalates have advantages such as high electronegativity, rich surface charge density, and excellent redox activity. However, when used as an adsorbent for adsorption experiments, due to high solubility and easy aggregation, the exposed active sites are few, which greatly limits further applications.

[0005] In view of this, the present invention is specifically proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a zeolite-structured polyoxometalate-based metal-organic framework material, a preparation method thereof, and an application thereof to solve the above problems.

[0007] To achieve the above object, the present invention specifically adopts the following technical solutions:

[0008] A preparation method of a zeolite-structured polyoxometalate-based metal-organic framework material, the preparation method comprising the following steps:

[0009] S1: Add (NH4)6Mo7O 24 ·4H2O, molybdenum powder and ZnCl2 to deionized water in sequence, disperse completely to obtain solution A;

[0010] S2: Add H3PO3, the template agent tetrabutylammonium hydroxide solution and the organic ligand imidazole to the solution A in sequence to obtain solution B, and adjust its pH to 5 - 5.5; preferably use 1M HCl to adjust the pH;

[0011] In the solution B, the mass ratio of the ZnCl2 to the organic ligand is 1:0.48 - 0.52; preferably 1:0.5;

[0012] The mass ratio of the (NH4)6Mo7O 24 ·4H2O to the H3PO3 is 1:0.03 - 0.04; preferably 1:0.032;

[0013] The mass ratio of the (NH4)6Mo7O 24 ·4H2O to the molybdenum powder is 1:0.08 - 0.12; preferably 1:0.097;

[0014] The mass ratio of the solute mass of the template agent to the (NH4)6Mo7O 24 ·4H2O is 0.1 - 0.2:1; preferably 0.1:1.

[0015] S3: Place the solution B in a reaction kettle, heat it up for reaction, cool it to room temperature after the reaction is completed, centrifuge to collect the initial reaction product, and activate the initial product with water and ethanol multiple times, and finally dry it to obtain the zeolite-structured polyoxometalate-based metal-organic framework material.

[0016] Preferably, the step S3 satisfies one or more of the following conditions:

[0017] a. The target temperature for the heating up is 453 - 473K;

[0018] b. The time for the heating up is 1 - 1.2h;

[0019] c. The time for the reaction is 40 - 45h;

[0020] d. The temperature reduction time for the cooling is 80 - 90h;

[0021] e. The drying includes: drying in a vacuum oven at 373 - 383K for 10 - 12h.

[0022] In this application, a zeolite polyoxometalate-based metal-organic framework material was in-situ synthesized by a one-step hydrothermal method using imidazole, Zn 2+ , ammonium molybdate, and phosphorous acid. In this material, the polyoxoacid cluster is composed of a central PO4 3- tetrahedron connected to the surrounding MoO6 octahedra through oxygen bridges; the nitrogen atoms on the imidazole ring coordinate with the zinc on the surface of the polyoxoacid cluster to form a stable three-dimensional structure.

[0023] This application provides a zeolite-structured polyoxometalate-based metal-organic framework material, which is prepared by the preparation method of the zeolite-structured polyoxometalate-based metal-organic framework material.

[0024] This application also provides an application of the zeolite-structured polyoxometalate-based metal-organic framework material prepared by the preparation method of the zeolite-structured polyoxometalate-based metal-organic framework material, which is used for adsorbing rubidium ions;

[0025] Preferably, the zeolite-structured polyoxometalate-based metal-organic framework material is suitable for the separation and enrichment of rubidium ions in complex water systems.

[0026] Metal-organic framework materials are porous crystalline materials formed by the self-assembly of metal ions, metal chains, or metal clusters with organic ligands through coordination bonds. By introducing size-matched polyoxoanions (POMs) into the MOF framework to replace metal ions or metal clusters therein, polyoxometalate-based metal-organic framework materials (abbreviated as POMOFs) with high surface activity and good crystallinity are constructed. The functional integration of POMs and MOFs is achieved. Specifically, the POMs unit can provide active sites for specific interactions with target molecules, and the porous structure of MOFs provides efficient transport channels and sufficient space for the diffusion and adsorption of target molecules.

[0027] In this application, a one-step hydrothermal method is adopted, using imidazole, Zn 2+ , ammonium molybdate, and phosphorous acid as raw materials to in-situ synthesize a zeolite-structured polyoxometalate-based metal-organic framework material, effectively overcoming the problems of high solubility and easy aggregation of polyacid components in aqueous solutions, contributing to the uniform distribution and stable embedding of active components in the material, thereby significantly improving the adsorption performance of the material for rubidium ions; compared with the conventional post-synthesis method, the one-step hydrothermal synthesis route in this application is simple, the process flow is more efficient, significantly reducing the complexity and error of experimental operations, significantly improving the experimental efficiency and repeatability; at the same time, by regulating the reaction conditions, the structural characteristics are precisely adjusted, which is beneficial to obtaining high-performance materials with good crystallinity and uniform functional distribution. The thermal stability, water stability, and anti-interference ion ability are significantly improved, and high adsorption performance can be maintained in a wide pH range, which is suitable for the separation and enrichment of rubidium ions in complex water systems.

[0028] Advantages of the present invention:

[0029] In this application, a one-step hydrothermal in-situ synthesis method is adopted to introduce polyoxometalate clusters into zeolitic imidazolate framework materials (ZIFs), obtaining zeolite-structured polyoxometalate-based metal-organic framework materials (Z-POMOF). Comparing it with the classical zeolitic imidazolate framework material ZIF-8, the results show that Z-POMOF retains the basic framework of ZIF-8, and compared with ZIF-8, Z-POMOF exhibits excellent adsorption performance and good selectivity for rubidium ions.

[0030] Through reasonable design and functional modification, MOF materials can achieve efficient and selective adsorption of rubidium ions, providing a new idea for solving the problems of rubidium resource shortage and environmental pollution. Description of the drawings

[0031] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0032] Figure 1 PXRD diagrams of the materials provided for the examples and comparative examples;

[0033] Figure 2 PXRD diagrams of the materials provided for Comparative Examples 2-3;

[0034] Figure 3 SEM diagrams of the materials provided for Example 1 and Comparative Example 2;

[0035] Figure 4 XPS analysis diagram of the surface elements of the material provided for Example 1;

[0036] Figure 5 FTIR diagrams of Z-POMOF and Im (imidazole) provided for Example 1;

[0037] Figure 6 TGA curve diagram of Z-POMOF provided for Example 1 in a nitrogen atmosphere;

[0038] Figure 7 Test result diagrams of the rubidium ion adsorption performance of the materials provided for the examples and comparative examples:

[0039] Figure 8(a) is the test result diagram of the adsorption isotherm of Z-POMOF provided for Example 1;

[0040] Figure 8(b) is the adsorption kinetics test result graph of Z-POMOF provided in Example 1;

[0041] Figure 9(a) is the adsorption result test graph of Z-POMOF provided in Example 1 in a binary ion mixed solution;

[0042] Figure 9(b) is the adsorption result test graph of Z-POMOF provided in Example 1 in a multi-ion mixed solution;

[0043] Figure 10 It is the test result graph of the stability and regeneration ability of the material provided in Example 1;

[0044] Figure 11 It is the mechanism result graph of the material provided in Example 1 for adsorbing Rb + ;

[0045] Figure 12 It is the synthesis route graph of the material provided in this application. Detailed implementation manners

[0046] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Apparently, the described embodiments are only a part rather than all of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0047] Example 1

[0048] This example provides a zeolite structure polyoxometalate-based metal-organic framework material and its preparation method, which are as follows:

[0049] S1: 0.618 g of (NH4)6Mo7O 24 ·4H2O, 0.060 g of molybdenum powder, and 0.136 g of ZnCl2 are successively added to 9 mL of deionized water, and after complete dispersion, solution A is obtained;

[0050] S2: 0.020 g of H3PO3, 256 μL of tetrabutylammonium hydroxide aqueous solution with a density of 0.973 g / mL and a mass concentration of 25% (w / w), and 0.068 g of imidazole are successively added to solution A obtained in S1 to obtain solution B;

[0051] S2-1: After stirring solution B evenly, the pH of solution B is adjusted to 5 - 5.5 with 1M HCl;

[0052] S3: Place the solution B obtained in S2-1 into a 25 mL polytetrafluoroethylene-lined reactor, heat it up for reaction, set the heating-up time to 1 h, the reaction temperature to 453 K, and the reaction time to 40 h. After the reaction is completed, cool it to room temperature, with the cooling-down time being 80 h. Then, centrifuge to collect the initial reaction product, and activate the initial product with water and ethanol successively for multiple times. Finally, dry it in a vacuum oven at 373 K for 12 h to obtain a zeolite-structured polyoxometalate-based metal-organic framework material, denoted as Z-POMOF.

[0053] Using imidazole, Zn 2+ , ammonium molybdate and phosphorous acid to in-situ synthesize a zeolite polyoxometalate-based metal-organic framework material. In this material, the polyoxoanion cluster is composed of a central PO4 3- tetrahedron and surrounding MoO6 octahedrons connected by oxygen bridges; the nitrogen atoms on the imidazole ring coordinate with zinc on the surface of the polyoxoanion cluster to form a stable three-dimensional structure. The specific synthesis process is as Figure 12 shown.

[0054] The PXRD pattern of the Z-POMOF prepared in this example is as Figure 1 shown, where Z-POMOF Sim. represents the PXRD result simulated from the single crystal structure of Z-POMOF, and Z-POMOF Exp. represents the PXRD result obtained experimentally.

[0055] Comparative Example 1

[0056] The difference from Example 1 is that the imidazole in S2 is replaced with 0.210 g of benzene-1,3,5-tricarboxylic acid, and the other steps are the same.

[0057] The prepared material is denoted as Z-POMOF-1, and the PXRD pattern is as Figure 1 shown. Z-POMOF-1Exp represents the PXRD result obtained experimentally for Z-POMOF-1.

[0058] Comparative Example 2

[0059] The material provided in this comparative example is ZIF-8, and the specific preparation method is as follows:

[0060] First, weigh 2.97 g of Zn(NO3)2·6H2O and 75 mL of methanol and place them in beaker A. Then, weigh 3.08 g of 2-methylimidazole and dissolve it in 75 mL of methanol and place it in beaker B. After stirring for 20 min respectively, slowly add the solution in beaker B to the solution in beaker A, stir at room temperature for 12 h, and let it stand for 12 h. Then, centrifuge to collect the white precipitate and activate it with methanol three times. Finally, transfer the activated product to a centrifuge tube and dry it in vacuum at 333 K for 12 h to obtain the target product ZIF-8, and the PXRD pattern is as Figure 1As shown, where ZIF-8Sim. represents the PXRD results obtained by simulating the single-crystal structure of ZIF-8, and ZIF-8Exp. represents the PXRD results obtained from the experiment of ZIF-8.

[0061] Comparative Example 3

[0062] This comparative example provides a material and its preparation method, which are as follows:

[0063] First, weigh 2.97 g of Zn(NO3)2·6H2O and 75 mL of methanol and place them in beaker A, ultrasonically disperse them evenly, then add 1 g of ammonium phosphomolybdate (AMP). Weigh 3.08 g of 2-methylimidazole and dissolve it in 75 mL of methanol and place it in beaker B. After stirring for 20 min respectively, slowly add the solution in beaker B to the solution in beaker A, stir at room temperature for 12 h, and let it stand for 12 h. Then, centrifuge to collect the white precipitate and activate it three times with methanol. Finally, transfer the activated product to a centrifuge tube and vacuum dry it at 333 K for 12 h to obtain the target product, denoted as ZIF-8@AMP-1.

[0064] According to the method of this comparative example, adjust the added mass of AMP to 2 g, 3 g, and 4 g respectively, and correspondingly obtain ZIF-8@AMP-2, ZIF-8@AMP-3, and ZIF-8@AMP-4.

[0065] Comparative Example 4

[0066] The difference from Example 1 is that the addition time of 0.020 g of H3PO3 is adjusted to step S1, and no H3PO3 is added in step S2.

[0067] The obtained product is denoted as Z-POMOF-2. The PXRD pattern is as Figure 1 shown. Z-POMOF-2Exp represents the PXRD results obtained from the experiment of Z-POMOF-2.

[0068] Figure 2 It is the PXRD pattern of the materials provided in Comparative Examples 2 - 3. Among them, ZIF-8@AMP-1Exp., ZIF-8@AMP-2Exp., ZIF-8@AMP-3Exp., and ZIF-8@AMP-4Exp. are the PXRD results obtained from the experiments of the products corresponding to different AMP loading masses respectively. ZIF-8Sim. represents the PXRD results obtained by simulating the single-crystal structure of ZIF-8, and ZIF-8Exp. represents the PXRD results obtained from the experiment of ZIF-8. AMP Exp. represents the PXRD results obtained from the experiment of AMP.

[0069] Figure 3 It is the SEM images of the materials provided in Example 1 and Comparative Example 2. Among them Figure 3(a) and Figure 3 (c) are SEM images of comparative example 2 at magnifications of 20,000 times and 100,000 times, respectively. ZIF-8 presents a typical rhombic dodecahedron shape with a diameter of 200-300 nm; Figure 3 (b) and Figure 3 (d) are SEM images of Example 1 at magnifications of 30,000 times and 150,000 times, respectively. Z-POMOF has a truncated dodecahedron morphology with a diameter of 100-200nm. In addition, in the SEM image at high magnification, it can be seen that ZIF-8 has a very smooth surface, while uniformly distributed particles can be observed on the surface of Z-POMOF. This is because the POM clusters are larger in volume (diameter of about 0.9-1.5nm), close to the pore size of ZIF-8 (1.2nm), and when they are introduced into the MOF structure, the ZIF skeleton changes from the original micropores to larger mesopores.

[0070] Figure 4 The surface element XPS analysis diagram of Z-POMOF provided in Example 1; wherein Figure 4 (a)-(f) are the detailed spectrum analysis of C1s, N 1s, O 1s, P 2p, Mo 3d and Zn 2p, respectively.

[0071] Figure 5 FTIR graph of Z-POMOF and Im (imidazole) provided in Example 1.

[0072] Figure 6 This is the TGA curve of the Z-POMOF provided in Example 1 under a nitrogen atmosphere.

[0073] The materials provided in the examples and comparative examples were subjected to performance tests: 5 mg of Z-POMOF provided in Example 1, Z-POMOF-1 provided in Comparative Example 1, ZIF-8 provided in Comparative Example 2, ZIF-8@AMP-1, ZIF-8@AMP-2, ZIF-8@AMP-3 and ZIF-8@AMP-4 provided in Comparative Example 3, and Z-POMOF-2 provided in Comparative Example 4 were weighed and added to 10 mL of a rubidium ion solution with an initial concentration of C0 = 55.52 mg / L. ICP-OES was used to measure the Rb content in the solution before and after adsorption. + The concentration of adsorption was calculated. The adsorption experimental conditions were: reaction temperature 298K, reaction time 24h. The experimental results are shown in Figure 7 ,Depend on Figure 7 It can be observed that under the same experimental conditions, the Z-POMOF provided by Example 1 has the largest adsorption capacity.

[0074] The Z-POMOF material provided in Example 1 was further analyzed. Multiple portions of 5 mg of the Z-POMOF prepared in Example 1 were weighed and added to 10 mL of rubidium ion solutions with different initial concentrations. ICP-OES was used to measure the concentration of Rb + in the solution before and after adsorption and calculate the maximum adsorption capacity. The adsorption experiment conditions were: reaction temperature 298 K, reaction time 24 h, and the initial concentration range of Rb + in the solution was 0 - 350 mg / L. The experimental results are shown in Figure 8(a); Multiple portions of 5 mg of the Z-POMOF prepared in Example 1 were weighed and added to 10 mL of rubidium ion solutions with equal concentrations. The adsorption experiment was stopped at different reaction times, and the concentration of Rb + in the solution before and after adsorption was measured and the adsorption capacity was calculated. The adsorption experiment conditions were: reaction temperature 298 K, and the initial concentrations of Rb + in the solution were C0 = 11.01 mg / L and 55.52 mg / L. The experimental results are shown in Figure 8(b). It can be observed from Figure 8(b) that the adsorption experiment can reach equilibrium within 5 minutes.

[0075] Testing the influence of different ions on adsorption: Multiple portions of 5 mg of the Z-POMOF prepared in Example 1 were weighed and added to 10 mL of binary / multicomponent ion mixed solutions. The coexisting ions were potassium, calcium, sodium, magnesium, lithium, and cesium respectively. The concentration of Rb + in the solution before and after adsorption was measured and the adsorption capacity was calculated. The adsorption experiment conditions were: reaction temperature 298 K, reaction time 24 h, and the initial concentrations of Rb + in the solution were (a) C0 = 55.76 mg / L and (b) C0 = 10.00 mg / L respectively. The experimental results are shown in Figure 9(a) and Figure 9(b) respectively. Among them, Figure 9(a) is the test diagram of the adsorption result of the Z-POMOF provided in Example 1 in the binary ion mixed solution; Figure 9(b) is the test diagram of the adsorption result of the Z-POMOF provided in Example 1 in the multicomponent ion mixed solution.

[0076] Testing the stability and regeneration ability of the material provided in Example 1: The adsorbent material Z-POMOF after adsorbing rubidium ions was eluted with 3 mol / L ammonium chloride solution to study the regeneration performance of the adsorbent material. The adsorption experiment conditions were: reaction temperature 298 K, reaction time 24 h, and the initial concentration of Rb + in the solution was C0 = 10.99 mg / L. The experimental results are shown in Figure 10 (a). Figure 10 (a) is the test diagram of the adsorption performance of the Z-POMOF material after adsorption after regeneration; Then, the PXRD conditions of the adsorption material before and after adsorption and after regeneration were studied, and the results are shown in Figure 10 (b). Figure 10(b) PXRD patterns of Z-POMOF before and after adsorption, and Z-POMOF after elution regeneration show that the crystal structure is not significantly damaged, demonstrating its reusability.

[0077] Study the adsorption mechanism of the material provided in Example 1 for Rb + : Conduct FTIR tests on the adsorbent material Z-POMOF, the adsorbent material Z-POMOF after adsorbing Rb + and the adsorbent material Z-POMOF after regeneration treatment with 3 mol / L ammonium chloride solution. The experimental results are shown in Figure 11 (a). It can be observed that the weakened diffraction peaks after adsorption recover to some extent after regeneration treatment; Measure the concentrations of Rb + and NH4 + in the solution before and after adsorption. The test results are shown in Figure 11 (b). It can be observed that the concentration of Rb + in the solution decreases after adsorption, and the concentration of NH4 + increases, indicating that the adsorption process of the adsorbent material Z-POMOF and Rb + involves ion exchange between NH4 + in the material and Rb + .

[0078] Please note that the technical features of the above embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as these combinations of technical features do not conflict, they should be considered as within the scope described in this specification. The above embodiments only represent several implementation manners of the present application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can still be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the appended claims.

Claims

1. A method for preparing a zeolite structure polyoxometalate-based metal organic framework material, characterized in that: The preparation method comprises the following steps: S1: Add (NH4)6Mo7O to deionized water in sequence 24 4H2O, molybdenum powder and ZnCl2 are dispersed completely to obtain solution A; S2: adding H3PO3, a template and an organic ligand to the solution A in sequence to obtain a solution B; S3: placing the solution B in a reactor and heating it to react, cooling it to room temperature after the reaction is completed, collecting the initial reaction product by centrifugation, and activating the initial product with water and ethanol in turn for multiple times, and finally drying it to obtain the zeolite structure polyoxometalate-based metal organic framework material.

2. The preparation method according to claim 1, characterized in that: The template agent includes tetrabutylammonium hydroxide solution; Preferably, the mass of the template solute is about the same as that of the (NH4)6Mo7O 24 The mass ratio of 4H2O is 0.1-0.2:

1.

3. The preparation method according to claim 1, characterized in that: The organic ligand includes imidazole.

4. The preparation method according to claim 1 or 3, characterized in that: The mass ratio of the ZnCl2 to the organic ligand is 1:0.48-0.

52.

5. The preparation method according to claim 1, characterized in that: The (NH4)6Mo7O 24 The mass ratio of 4H2O to the H3PO3 is 1:0.03-0.

04.

6. The preparation method according to claim 1, characterized in that: The (NH4)6Mo7O 24 The mass ratio of 4H2O to the molybdenum powder is 1:0.08-0.

12.

7. The preparation method according to claim 1, characterized in that: The preparation method further comprises: before step S3, adjusting the pH of solution B prepared in step S2 to 5-5.

5.

8. The preparation method according to claim 1, characterized in that: The step S3 satisfies one or more of the following conditions: a. The target temperature of the heating is 453-473K; b. The heating time is 1-1.2h; c. The reaction time is 40-45h; d. The cooling time is 80-90h; e. The drying comprises: drying in a vacuum oven at 373-383K for 10-12h.

9. A zeolite structure polyoxometalate-based metal organic framework material, characterized in that: The zeolite structure polyoxometalate-based metal organic framework material is prepared by the preparation method of the zeolite structure polyoxometalate-based metal organic framework material according to any one of claims 1 to 7.

10. An application of a zeolite structure polyoxometalate-based metal organic framework material prepared by the method for preparing a zeolite structure polyoxometalate-based metal organic framework material according to any one of claims 1 to 7, characterized in that: It is used to adsorb rubidium ions; The zeolite structure polyoxometalate-based metal organic framework material is suitable for separation and enrichment of rubidium ions in complex water systems.

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